Using the first-principles calculations based on density functional theory, the important role of electrode materials in determining the interfacial, ferroelectric stability and magnetoelectric properties in BaTiO3-based multiferroic tunnel junctions (MFTJs) have been investigated comparatively. It is found that the SrO–TiO2 interface of MFTJs with oxide electrode SrRuO3 is the most favorable interfacial structure. The average ferroelectric polarizations of MFTJs with electrode Co, FeCo and SrRuO3 are 25, 36 and 0 μC/cm2, respectively. The using of alloy electrode FeCo is more contributed to ferroelectric stability and the enhancement of magnetoelectric coupling of BaTiO3-based MFTJs. We expect our findings can provide an essential evaluation for the selection of electrode materials in spintronic storage devices.